Ethylenically unsaturated compounds containing 1-hydrocarbyloxy-2,2,6,6-tetramethylpiperidine moieties, and polymers, copolymers and stabilized compositions

ABSTRACT

Ethylenically unsaturated compounds containing 1-hydrocarbyloxy-2,2,6,6-tetramethylpiperidine moieties represent reactable stabilizers which may be homopolymerized or copolymerized with other ethylenically saturated monomers to form non-migrating, light stabilizers which are very effective in stabilizing polyolefins and other polymer substrates against the deleterious effects of actinic light.

This is a divisional of Ser. No. 605,636 filed 10/30/90 which is adivisional of Ser. No. 479,912 filed 2/14/90 which is acontinuation-in-part of Ser. No. 326,705 filed 3/21/89 now abandoned.

The instant invention is to ethylenically unsaturated compoundscontaining 1-hydrocarbyloxy-2,2,6,6-tetramethylpiperidine moieties topolymers and copolymers made therefrom and to polymer compositionsstabilized against the deleterious effects of actinic light bycontaining a stabilizing amount of said compounds.

BACKGROUND OF THE INVENTION

Monomeric copolymerizable light stabilizers which contain a hinderedamine moiety are known in the art as the following list of typicalpatents and publications attest: U.S. Pat. Nos. 4,294,949; 4,210,612;4,743,657; and F. Karrer, Makromol. Chem. 181, 595 (1980); K. W. Lee etal, J. Polym. Science, Poly Chem. Ed, 10, 3295 (1972); and T. Kuvosakiet al, J. Polym. Science, Poly. Chem. Ed, 12, 1407 (1974).

None of the above references discloses or suggests the instant compoundssubstituted on the 1-N atom by a hydrocarbyloxy group.

Non-polymerizable hindered amines substituted on the 1-N atom byhydrocarbyloxy groups are described in copending patent applicationsSer. Nos. 259,956; 099,418; 59,950; 259,958; 259,945; 259,944; 259,952;259,949; 59,955 and 259,946. However, the compounds described in thesecopending applications cannot be homopolymerized or copolymerized thuslosing a key element of versatility available to the instantethylenically unsaturated materials.

OBJECTS OF THE INVENTION

One object of the instant invention is to provide an ethylenicallyunsaturated, polymerizable monomer containing a hindered amine moietysubstituted on the 1-N atom with a hydrocarbyloxy group.

Another object of the instant invention is to provide homopolymers ofsaid monomers which have increased resistance to migration and to lossdue to volatilization under end use conditions.

Still another object of this invention is to describe copolymers of saidmonomers with a wide variety of other ethylenically unsaturated monomershaving no hindered amine moiety.

Yet another object of the invention is to provide polymer compositionswhich are stabilized against the deleterious effects of actinic light byhaving, present a stabilizing amount of said monomer or of a polymerprepared from said monomer.

DETAILED DISCLOSURE

The instant invention is to an ethylenically unsaturated, polymerizablemonome containing a hindered amine moiety substituted on the 1-N atomwith a hydroxycarbyloxy group, said moiety having the formula E ##STR1##where L₁ and L₂ are independently alkyl of 1 to 4 carbon atoms, or L₁and L₂ together are pentamethylene, and R₁ is hydrocarbyl, and saidmonomer is selected from the group consisting of formula I-IX ##STR2##where R₁ is alkyl of 1 to 36 carbon atoms, alkenyl of 2 to 18 carbonatoms, alkynyl of 2 to 18 carbon atoms, aralkyl of 7 to 15 carbon atoms,cycloalkyl of 5 to 12 carbon atoms, cycloalkenyl of 5 to 12 carbonatoms, a radical of a saturated or unsaturated bicyclic or tricyclichydrocarbon of 7 to 12 carbon atoms, or aryl of 6 to 10 carbon atoms orsaid aryl substituted by alkyl,

X is a direct bond, --O(polyoxyalkyleneO)-- of 2 to 12 carbon atoms,--O--, --NH----or --NG--, where G is alkyl of 1 to 8 carbon atoms,

X₁ is a direct bond or --O--,

n is 1 or 2,

T₁, T₂ and T₄ are independently hydrogen, halogen, alkyl of 1 to 18carbon atoms or aryl of 6 to 10 carbon atoms,

T₃ is hydrogen or methyl, and

R₂, R₃ and R₄ are independently hydrogen or alkyl of 1 to 12 carbonatoms, or R₂ is also cyano in formula III.

Preferably L₁ and L₂ are each methyl.

Preferably R₁ is alkyl of 1 to 18 carbon atoms, alkenyl of 2 to 3 carbonatoms, propargyl, benzyl or cyclohexyl.

G is preferably alkyl of 1 to 4 carbon atoms.

Preferably T₁ and T₂ are both hydrogen.

Preferably T₃ is hydrogen.

Preferably R₂, R₃ and R₄ are each hydrogen or R₃ and R₄ are hydrogen andR₂ is methyl.

When R₁ is alkyl, R₁ is, for example, methyl, ethyl, butyl, amyl, octyl,nonyl, dodecyl tetradecyl, octadecyl, eicosyl, tricosyl or tricontyl.

When R₁ is alkenyl, R₁ is for example, vinyl, allyl, octenyl or oleyl.

When R₁ is alkynyl, R₁ is, for example propargyl.

When R₁ is cycloalkyl, R₁ is for example, cyclopentyl, cyclohexyl,cyclooctyl or cyclododecyl.

Each of the monomers of formulas I to IX contains an ethylenicallyunsaturated group allowing the monomer to polymerize using free radicalinitiation, photoinitiation, group transfer polymerization, graftpolymerization, or cationic or anionic polymerization to prepare eithera homopolymer or a copolymer when more than one monomer of formula I toIX are copolymerized together.

Further, each of the monomers of formulas I to IX may be copolymerizedwith a separate vinyl monomer having no group of formula E present toyield a copolymer having as an integral part of the polymer backbonestabilizing units having pendant groups of formula E attached thereto.

Said polymer or copolymer comprises the polymerization product of (a) 1to 100% by weight, based on the total polymer or copolymer, of at leastone ethylenically unsaturated, polymerizable, monomer containing ahindered amine moiety substituted on the 1-N atom with a hydrocarbyloxygroup, said moiety having the formula E ##STR3## where L₁ and L₂ areindependently alkyl of 1 to 4 carbon atoms or L₁ and L₂ together arepentamethylene, and R₁ is hydrocarbyl, and said monomer is selected fromthe group consisting of formulas I-IX ##STR4## where R₁ is alkyl of 1 to36 carbon atoms, alkenyl of 2 to 18 carbon atoms, alkynyl of 2 to 18carbon atoms, aralkyl of 7 to 15 carbon atoms, cycloalkyl of 5 to 12carbon atoms, cycloalkenyl of 5 to 12 carbon atoms, a radical of asaturated or unsaturated bicyclic or tricyclic hydrocarbon of 7 to 12carbon atoms, or aryl of 6 to 10 carbon atoms or said aryl substitutedby alkyl,

X is a direct bond, --O(polyoxyalkyleneO)-- of 2 to 12 carbon atoms,--O--, --NH----or --NG--, where G is alkyl of 1 to 8 carbon atoms,

X₁ is a direct bond or --O--,

n is 1 or 2,

T₁, R₂ and R₄ are independently hydrogen, halogen, alkyl of 1 to carbonatoms or aryl of 6 to 10 carbon atoms,

T₃ is hydrogen or methyl, and

R₂, R₃ and R₄ are independently hydrogen or alkyl of 1 to 12 carbonatoms, or R₂ is also cyano in formula III.

(b) 99 to 0% by weight, based on the total polymer or copolymer, of atleast one ethylenically unsaturated, polymerizable monomer having nogroup of formula E present and selected from the group consisting of theesters and amides of acrylic and methacrylic acid, the itaconates, thecitraconates, styrene, the vinyl pyridines, divinylbenzene,acrylonitrile, methacrylonitrile, N-vinyl-2-pyrrolidone,N-vinylcarbazole, maleimides, vinyl sulfonate, vinyl phosphonates,alpha-olefins, isoprene, butadiene, vinyl esters, vinyl ethers andhalogenated olefins.

Such copolymers, having even a small quantity of component (a) present,would have built in a high degree of light stabilizing units whichcannot migrate, be lost by volatilization or otherwise leave the crucialsite for protecting the copolymer from the deleterious effects ofactinic light.

A still further aspect of the instant invention are stabilizedcompositions which comprise

(A) an organic polymer subject to the deleterious effects of actiniclight, and

(B₁) a stabilizing amount of an ethylenically unsaturated, polymerizablemonomer containing a hindered amine moiety substituted on the 1-N atomwith a hydrocarbyloxy group, said moiety having the formula E ##STR5##where L₁ and L₂ are independently alkyl of 1 to 4 carbon atoms, or L₁and L₂ together are pentamethylene, and R₁ is hydrocarbyl, and saidmonomer is selected from the group consisting of formulas I-IX ##STR6##where R₁ is alkyl of 1 to 36 carbon atoms, alkenyl of 2 to 18 carbonatoms, alkynyl of 2 to 18 carbon atoms, aralkyl of 7 to 15 carbon atoms,cycloalkyl of 5 to 12 carbon atoms, cycloalkenyl of 5 to 12 carbonatoms, a radical of a saturated or unsaturated bicyclic or tricyclichydrocarbon of 7 to 12 carbon atoms, or aryl of 6 to 10 carbon atoms orsaid aryl substituted by alkyl,

X is a direct bond, --O(polyoxyalkyleneO)-- of 2 to 12 carbon atoms,--O--, --NH----or --NG--, where G is alkyl of 1 to 8 carbon atoms,

X₁ is a direct bond or --O--,

n is 1 or 2,

R₁, R₂ and R₄ are independently hydrogen, halogen, alkyl of 1 to 18carbon atoms or aryl of 6 to 10 carbon atoms,

T₃ is hydrogen or methyl, and

R₂, R₃ and R₄ are independently hydrogen or alkyl of 1 to 12 carbonatoms; or R₂ is also cyano in formula III; or

(B₂) a stabilizing amount of a polymer or copolymer which comprises thefree radical polymerization product of

(a) 1 to 100% by weight, based on the total polymer or copolymer, of atleast one ethylenically unsaturated polymerizable monomer containing ahindered amine moiety substituted on the 1-N atom with a hydrocarbyloxygroup, said moiety having the formula E ##STR7## where L₁ and L₂ areindependently alkyl of 1 to 4 carbon atoms, or L₁ and L₂ together arepentamethylene, and R₁ is hydrocarbyl, and said monomer is selected fromthe group consisting of formulas I-IX ##STR8## where R₁ is alkyl of 1 to36 carbon atoms, alkenyl of 2 to 18 carbon atoms, alkynyl of 2 to 18carbon atoms, aralkyl of 7 to 15 carbon atoms, cycloalkyl of 5 to 12carbon atoms, cycloalkenyl of 5 to 12 carbon atoms, a radical of asaturated or unsaturated bicyclic or tricyclic hydrocarbon of 7 to 12carbon atoms, or aryl of 6 to 10 carbon atoms or said aryl substitutedby alkyl,

X is a direct bond, --O(polyoxyalkyleneO)-- of 2 to 12 carbon atoms,--O--, --NH----or --NG--, where G is alkyl of 1 to 8 carbon atoms,

X₁ is a direct bond or --O--,

n is 1 or 2,

T₁, T₂ and T₄ are independently hydrogen, halogen, alkyl of 1 to 18carbon atoms or aryl of 6 to 10 carbon atoms,

T₃ is hydrogen or methyl, and

R₂, R₃ and R₄ are independently hydrogen or alkyl of 1 to 12 carbonatoms, or R₂ is also cyano in formula III; and

(b) 99 to 0% by weight, based on the total polymer or copolymer, of atleast one ethylenically unsaturated, polymerizable monomer having nogroup of formula E present and selected from the group consisting of theesters and amides of acrylic and methacrylic acid, the itaconates, thecitraconates, styrene, the vinyl pyridines, divinylbenzene,acrylonitrile, methacrylonitrile, N-vinyl-2-pyrrolidone,N-vinylcarbazole, maleimides, vinyl sulfonate, vinyl phosphonates,alpha-olefins, isoprene, butadiene, vinyl esters, vinyl ethers andhalogenated olefins.

The ethylenically unsaturated comonomers may also contain a UV-absorbingmoiety such as a hydroxyphenyl substituted benzotriazole or s-triazine,a hydroxy substituted benzophenone, an oxanilide oralpha-cyanocinnamate. Examples of such ethylenically unsaturatedUV-absorbers are described in a number of United States patents whichare hereby incorporated into this application by references.

Acrylated benzotriazoles are described in U.S. Pat. Nos. 4,413,095;4,716,234; 4,785,063 and 4,803,254. Acryloxyalkyl benzotriazoles aredescribed in U.S. Pat. No. 4,260,768. Vinyl substituted benzotriazolesare described in U.S. Pat. No. 4,508,882. Ethylenically unsaturatedbenzotriazoles are described in U.S. Pat. No. 3,493,539. Acrylatedbenzophenones are described in U.S. Pat. No. 4,310,650.

There are several synthetic procedures which can be used to prepare theinstant compounds.

These include:

(a) transesterification using a 4-hydroxy-2,2,6,6-tetramethylpiperidineand a lower alkyl ester of a unsaturated acid such as acrylic, fumaric,muconic or the like;

(b) esterification using a 4-hydroxy-2,2,6,6-tetramethylpiperidine andan acid chloride such as acryloyl or methacryloyl chloride;

(c) amidation using a 4-amino-2,2,6,6-tetramethylpiperidine and an acidchloride such as acryloyl or methacryloyl chloride;

(d) imidation using a 4-amino-2,2,6,6-tetramethylpiperidine and a cyclicanhydride such as maleic anhydride followed by cyclization of theintermediate maleamic acid;

(e) halide displacement using an unsaturated benzyl

The intermediates needed to prepare the instant compounds ar elargelyitems of commerce or can be made by conventional methods known in theart.

Typical compounds of the isntant invention include the following:

    ______________________________________                                         ##STR9##                                                                     R         R.sub.1     X            R.sub.2                                    ______________________________________                                        H         allyl       O            H                                          H         allyl       NH           methyl                                     H         cyclohexyl  O            methyl                                     H         methyl      O            H                                          H         methyl      N(n-butyl)-  H                                          methyl    octyl       O            H                                          H         methyl      NH           H                                          H         methyl      NH           methyl                                     H         cyclohexyl  N(n-butyl)-  methyl                                     H         cyclohexyl  NH           methyl                                     H         octadecyl   O            methyl                                     H         benzyl      O            H                                          H         octyl       O            methyl                                     methyl    octyl       O            methyl                                     H         octyl       NH           H                                          H         octyl       N(n-butyl)-  methyl                                     H         octyl       NH           methyl                                     ______________________________________                                         ##STR10##                                                                    R             R.sub.1       R.sub.2                                           ______________________________________                                        H             cyclohexyl    methyl                                            H             methyl        H                                                 H             methyl        methyl                                            H             cyclohexyl    H                                                 H             octyl         H                                                 H             octyl         methyl                                            methyl        octyl         methyl                                            H             allyl         H                                                 H             allyl         methyl                                            H             octadecyl     H                                                 H             octadecyl     methyl                                            ______________________________________                                         ##STR11##                                                                    R          R.sub.1     T.sub.1    T.sub.2                                     ______________________________________                                        H          methyl      H          H                                           H          cyclohexyl  H          dodecyl                                     H          methyl      H          dodecyl                                     H          octyl       H          H                                           H          octyl       methyl     methyl                                      methyl     octyl       methyl     methyl                                      H          octyl       H          dodecyl                                     H          allyl       H          H                                           H          allyl       H          methyl                                      H          octadecyl   H          H                                           ______________________________________                                         ##STR12##                                                                           R            R.sub.1                                                   ______________________________________                                               H            methyl                                                           H            cyclohexyl                                                       H            octyl                                                            H            octadecyl                                                        methyl       octyl                                                            H            allyl                                                     ______________________________________                                         ##STR13##                                                                    R          R.sub.1     N        X                                             ______________________________________                                        H          cyclohexyl  1        O                                             H          cyclohexyl  2        O                                             H          methyl      1        O                                             methyl     octyl       1        O                                             methyl     octyl       2        O                                             H          octyl       1        O                                             H          octyl       2        O                                             H          allyl       1        O                                             H          octadecyl   1        O                                             H          cyclohexyl  1        NH                                            H          cyclohexyl  1        N(n-butyl)-                                   H          methyl      1        NH                                            H          methyl      1        N(n-butyl)-                                   H          octyl       1        NH                                            H          octyl       1        N(n-butyl)-                                   H          allyl       1        N(n-butyl)-                                   H          octadecyl   1        N(n-butyl)-                                   ______________________________________                                    

Although the instant application emphasizes the2,2,6,6-tetralkylpiperidine structure, it is to be noted that theinvention also relates to compounds wherein the following tetraalkylsubstituted piperazine or piperazinone moieties are substituted for theabove-noted tetralkylpiperidine moiety: ##STR14## wherein M and Y areindependently methylene or carbonyl, preferably M being methylene and Ybeing carbonyl. It is understood that the identified substituentsapplicable to such compounds are those which are appropriate forsubstitution on the ring nitrogen atoms.

Substrates in which the compounds of this invention are particularlyuseful are polyolefins such as polyethylene and polypropylene;polystyrene, including especially impact polystyrene; ABS resin;elastomers such as e.g. butadiene rubber, EPM, EPDM, SBR and nitrilerubber.

In general polymers which can be stabilized include

1. Polymers of monoolefins and diolefins, for example polyethylene(which optionally can be crosslinked), polypropylene, polyisobutylene,polybutene-1, polymethylpentene-1, polyisoprene or polybutadiene, aswell as polymers of cycloolefins, for instance of cyclopentene ornorbornene.

2. Mixtures of the polymers mentioned under 1), for example mixtures ofpolypropylene with polyisobutylene.

3. Copolymers of monoolefins and diolefins with each other or with othervinyl monomers, such as, for example, ethylene/propylene,propylene/butene-1, propylene/isobutylene, ethylene/butene-1,propylene/butadiene, isobutylene/isoprene, ethylene/alkyl acrylates,ethylene/alkyl methacrylates, ethylene/vinyl acetate or ethylene/acrylicacid copolymers and their salts (ionomers) and terpolymers of ethylenewith propylene and a diene, such as hexadiene, dicyclopentadiene orethylidene-norbornene.

4. Polystyrene, poly-(p-methylstyrene).

5. Copolymers of styrene or methylstyrene with dienes or acrylicderivatives, such as, for example, styrene/butadiene,styrene/acrylonitrile, styrene/ethyl methacrylate,styrene/butadiene/ethyl arylate, styrene/acrylonitrile/methyl acrylate;mixtures of high impact strength from styrene copolymers and anotherpolymer, such as, for example, from a polyacrylate, ad iene polymer oran ethylene/propylene/diene terpolymer; and block polymers of styrene,such as, for example, styrene/butadiene/styrene,styrene/isoprene/styrene, styrene/ethylene/butylene/styrene orstyrene/ethylene/propylene/styrene.

6. Graft copolymers of styrene, such as, for example, styrene onpolybutadiene, styrene and acrylonitrile on polybutadiene, styrene andalkyl acrylates or methacrylates on polybutadiene, styrene andacrylonitrile on ethylene/propylene/diene terpolymers, styrene andacrylonitrile on polyacrylates or polymethacrylates, styrene andacrylonitrile on acrylate/butadiene copolymers, as well as mixturesthereof with the copolymers listed under (5), for instance the copolymermixtures known as ABS-, MBS-, ASA- or AES-polymers.

7. Halogen-containing polymers, such as polychloroprene, chlorinatedrubbers, chlorinated or sulfochlorinated polyethylene, epichlorohydrinhomo- and copolymers, polymers from halogen-containing vinyl compounds,as for example, polyvinylchloride, polyvinylidne chloride, polyvinylfluoride, polyvinylidene fluoride, as well as copolymers thereof, as forexample, vinyl chloride/vinylidene chloride, vinyl chloride/vinylacetate, vinylidene chloride/vinyl acetate copolymers, or vinylfluoride/vinyl ether copolymers.

8. Polymers which are derived from α,β-unsaturated acids and derivativesthereof, such as polyacrylates and polymethacrylates, polyacrylamide andpolyacrylonitrile.

9. Copolymers from the monomers mentioned under (8) with each other orwith other unsaturated monomers, such as, for instance,acrylonitrile/butadiene, acrylonitrile/alkyl acrylate,acrylonitrile/alkoxyalkyl acrylate or acrylonitrile/vinyl halogenidecopolymers or acrylonitrile/alkyl methacrylate/butadiene terpolymers.

10. Polymers which are derived from unsaturated alcohols and amines, oracyl derivatives thereof or acetals thereof, such as polyvinyl alcohol,polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinylmaleate, polyvinylbutyral, polyallyl phthalate or polyallyl-melamine.

11. Homopolymers and copolymers of cyclic ethers, such as polyalkyleneglycols, polyethylene oxide, polypropylene oxide or copolymers thereofwith bis-glycidyl ethers.

12. Polyacetals, such as polyoxymethylene and those polyoxymethyleneswhich contain ethylene oxide as comonomer.

13. Polyphenylene oxides and sulfides, and mixtures of polyphenyleneoxides with polystyrene.

14. Polyurethanes which are derived from polyethers, polyesters orpolybutadienes with terminal hydroxyl groups on the one side andaliphatic or aromatic polyisocyanates on the other side, as well asprecursors thereof (polyisocyanates, polyols or prepolymers).

15. Polyamides and copolyamides which are derived from diamines anddicarboxylic acids and/or from aminocarboxylic acids or thecorresponding lactams, such as polyamide 4, polyamide 6, polyamide 6/6,polyamide 6/10, polaymide 11, polyamide 12,poly-2,4,4-trimethylhexamethylene terephthalamide, poly-p-phenyleneterephthalamide or poly-m-phenylene isophthalamie, as well as copolymersthereof with polyethers, such as for instance with polyethylene glycol,polypropylene glycol or polytetramethylene glycols.

16. Polyureas, polyimides and polyamide-imides.

17. Polyesters which are derived from dicarboxylic acids and diolsand/or from hydroxycarboyxlic acids or the corresponding lactones, suchas polyethylene terephthalate, polybutylene terephthalate,poly-1,4-dimethylol-cyclohexane terephthalate,poly-[2,2-(4-hydroxyphenyl)-propane] terephthalate andpolyhydroxybenzoates as well as block-copolyether-esters derived frompolyethers having hydroxyl end groups.

18. Polycarbonates.

19. Polysulfones, polyethersulfones and polyetherketones.

20. Crosslinked polymers which are derived from aldehyes on the one handand phenols, ureas and melamines on the other hand, such asphenol/formaldehyde resins, urea/formaldehyde resins andmealmine/formaldehyde resins.

21. Drying and non-drying alkyd resins.

22. Unsaturated polyester resins which are derived from copolyesters ofsaturated and unsaturated dicarboxylic acids with polyhydric alcoholsand vinyl compounds as crosslinking agents, and also halogen-containingmodifications thereof of low flammability.

23. Thermosetting acrylic resins, derived from substituted acrylicesters, such as epoxy-acrylates, urethane-scrylates orsilicone-acrylates.

24. Alkyd resins, polyester resins or acrylate resins in admixture withmelamine resins, urea resins, polyisocyanates or epoxide resins ascrosslinking agents.

25. Crosslinked epoxide resins which are derived from polyepoxides, forexample from bis-glycidyl ethers or from cycloaliphatic diepoxides.

26. Natural polymers, such as cellulose, rubber, gelatin and derivativesthereof which are chemically modified in a polymer homologous manner,such as cellulose acetates, cellulose propionates and cellulosebutyrates, or the cellulose ethers, such as methyl cellulose.

27. Mixtures of polymers as mentioned above, for example PP/EPDM,Polyamide 6/EPDM or ABS, PVC/EVA, PVC/ABS, PVS/MBS, PC/ABS, PBTP/ABS.

28. Naturally occuring and synthetic organic materials which are puremonomeric compounds or mixtures of such compounds, for example mineraloils, animal and vegetable fats, oil and waxes, or oils, fats and waxesbased on synthetic esters (e.g. phthalates, adipates, phosphates ortrimellitates) and also mixtures of synthetic esters with mineal oils inany weight ratios, which materials may be used as plasticizers forpolymers or as textile spinning oils, as well as aqueous emulsions ofsuch materials.

29. Aqueous emulsions of natural or synthetic rubber, e.g. natural latexor latices of carboxylated styrene/butadiene copolymers.

30. Polysiloxanes such as the soft, hydrophilic polysiloxanes described,for example, in U.S. Pat. No. 4,259,467; and the hardpolyorganosiloxanes described, for example, in U.S. Pat. No. 4,355,147.

31. Polyketimines in combination with unsaturated acrylicpolyacetoacetate resins or with unsaturated acrylic resins. Theunsaturated acrylic resins include the urethane acrylates, polyetheracrylates, vinyl or acryl copolymers with pendant unsaturated groups andthe acrylated melamines. The polyketimines are prepared from polyaminesand ketones in the presence of an acid catalyst.

32. Radiation curable compositions containing ethylenically unsaturatedmonomers or oligomers and a polyunsaturated aliphatic oligomer.

33. Epoxymelamine resins such as light-stable epoxy resins crosslinkedby an epoxy functional coetherified high solids melamine resin such asLSE 4103 (Monsanto).

In general, the compounds of the present invention are employed in fromabout 0.01 to about 5% by weight of the stabilized composition, althoughthis will vary with the particular substrate and application. Anadvantageous range is from about 0.5 to about 2%, and especially 0.1 toabout 1%.

The stabilizers of the instant invention may readily be incorporatedinto the organic polymers by conventional techniques, at any convenientstage prior to the manufacture of shaped articles therefrom. Forexmaple, the stabilizer may be mized with the polymer in dry powderform, or a suspension or emulsion of the stabilizer may be mixed with asolution, suspension, or emulsion of the polymer. The resultingstabilized polymer compositions of the invention may optionally alsocontain various conventional additives, such as the following.

1. Antioxidants 1.1. Alkylated monophenols, for example,

2,6-di-tert-butyl-4-methylphenol

2-tert-butyl-4,6-dimethylphenol

2,6-di-tert-butyl-4-ethylphenol

2,6-di-tert-butyl-4-n-butylphenol

2,6-di-tert-butyl-i-butylphenol

2,6-di-cyclopentyl-4-methylphenol

2-(α-methylcyclohexyl)-4,6-dimethylphenol

2,6-di-octadecyl-4-methylphenol

2,4,6-tri-cyclohexylphenol

2,6-di-tert-butyl-4-methoxymethylphenol

1.2. Alkylated hydroquinones, for example,

2,6-di-tert-butyl-4-methoxyphenol

2,6-di-tert-butyl-hydroquinone

2,5-di-tert-amyl-hydroquinone

2,6-diphneyl-4-octadecyloxyphenol

1.3. Hydroxylated thiodiphenyl ethers, for example

2,2'-thio-bis-(6-tert-butyl-4-methylphenol)

2,2'-thio-bis-(4-octylphenol)

4,4'-thio-bis-(6-tert-butyl-3-methylphenol)

5,5'-thio-bis-(6-tert-butyl-2-methylphenol)

1.4. Alkylidene-bisphenols, for example,

2,2'-methylene-bis-(6-tert-butyl-4-methylphenol)

2,2'-methylene-bis-(6-tert-butyl-4-ethylphenol)

2,2'-methylene-bis-[4-methyl-6(α-methylcyclohexyl)-phenol)]

2,2'-methylene-bis-(4-methyl-6-cyclohexylphenol)

2,2'-methylene-bis-(6-nonyl-4-methylphenol)

2,2'-methylene-bis-[6-(α-methylbenzyl)-4-nonylphenol]

2,2'-methylene-bis-[6-(α,α-dimethylbenzyl)-4-nonylphenol]

2,2'-methylene-bis-(4,6-di-tert-butylphenol)

2,2'-ethylene-bis-(4,6-di-tert-butylphenol)

2,2'-ethylene-bis-(6-tert-butyl-4-isobutylphenol)

4,4'-methylene-bis-(2,6-di-tert-butylphenol)

4,4'-methylene-bis-(6-tert-butyl-2-methylphenol)

1,1-bis-(5-tert-butyl-4-hydroxy-2-methylphenyl-butane

2,6-di-(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol1,1,3-tris-(5-tert-butyl-4-hydroxy-2-methylphenyl)-butane

1,1-bis-(5-tert-butyl-4-hydroxy-2-methylphenyl)-3-n-dodecylmercaptobutane

ethyleneglycol bis-[3,3-bis-(3'-tert-butyl-4'-hydroxyphenyl)-butyrate]

di-(3-tert-butyl-4-hydroxy-5-methylphenyl)-dicyclopentadiene

di-[2-(3'-tert-butyl-2'-hydroxy-5'-methyl-benzyl)-6-tert-butyl-4-methylphenyl]terephthalate.

1.5. Benzyl compounds, for example,

1,3,5-tri-(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene

di-(3,5-di-tert-butyl-4-hydroxybenzyl) sulfide

3,5-di-tert-butyl-4-hydroxybenzyl-mercapto-acetic acid isooctyl ester

bis-(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithiol terephthalate

1,3,5-tris-(3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate

1,3,5-tris-(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate

3,5-di-tert-butyl-4-hydroxybenzyl-phosphoric acid dioctadecyl ester

3,5-di-tert-butyl-4-hydroxybenzyl-phosphoric acid monoethyl ester,calcium-salt

1.6. Acylaminophenols, for example,

4-hydroxy-lauric acid anilide

4-hydroxy-stearic acid anilide

2,4-bis-octylmercapto-6-(3,5-tert-butyl-4-hydroxyanilino)-s-triazine

octyl-N-(3,5-di-tert-butyl-4-hydroxyphenyl)-carbamate

1.7. Esters of β-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionic acid withmonohydric or polyhydric alcohols, for example,

    ______________________________________                                        methanol        diethylene glycol                                             octadecanol     triethylene glycol                                            1,6-hexanediol  pentaerythritol                                               neopentyl glycol                                                                              tris-hydroxyethyl isocyanurate                                thiodiethylene glycol                                                                         di-hydroxyethyl oxalic acid                                                   diamide                                                       ______________________________________                                    

1.8. Esters of 8-(5-tert-butyl-4-hydroxy-3-methylphenyl)-propionic acidmonohydric or polyhydric alcohols, for example,

    ______________________________________                                        methanol        diethylene glycol                                             octadecanol     triethylene glycol                                            1,6-hexanediol  pentaerythritol                                               neopentyl glycol                                                                              tris-hydroxyethyl isocyanurate                                thiodiethylene glycol                                                                         di-hydroxyethyl oxalic acid                                                   diamide                                                       ______________________________________                                    

1.9. Amides of β-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionic acid forexample,

N,N'-di-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hexamethylenediamine

N,N'-di-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-trimethylenediamine

N,N'-di-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hydrazine

2. UV absorbers and light stabilizers

2.1. 2-(2'-Hydroxyphenyl)-benzotriazoles, for example, the 5'-methyl-,3',5'-di-tert-butyl-, 5'-tert-butyl-, 5'-(1,1,3,3-tetramethylbutyl)-,5-chloro-3',5'-di-tert-butyl-, 5-chloro-3'-tert-butyl-5'-methyl-,3'-sec-butyl-5'-tert-butyl-, 4'-octoxy, 3',5'-di-tert-amyl-,3',5'-bis-(α,α-dimethylbenzyl),3'-tert-butyl-5'-(2-(omega-hydroxyocta-(ethyleneoxy)carbonyl-ethyl)-,3'-dodecyl-5'-methyl-, and 3'-tert-butyl-5'-(2-octyloxycarbonyl)ethyl-,and dodecylated-5'-methyl derivatives.

2.2. 2-Hydroxy-benzophenones, for example, the 4-hydroxy-, 4-methoxy-,4-octoxy, 4-decyloxy-, 4-dodecyloxy-, 4-benzyloxy, 4,2',4'-trihydroxy-and 2'-hydroxy-4,4'-dimethoxy derivatives.

2.3. Esters of optionally substituted benzoic acids for example, phenylsalicylate, 4-tert-butylphenyl salicylate, octylphenyl salicylate,dibenzoylresorcinol, bis-(4-tert-butylbenzoyl)-resorcinol,benzoylresorcinol, 3,5-di-tert-butyl-4-hydroxybenzoic acid2,4-di-tert-butylphenyl ester and 3,5-di-tert-butyl-4-hydroxybenzoicacid hexadecyl ester.

2.4. Acrylates, for example α-cyano-β,β-diphenylacrylic acid ethyl esteror isooctyl ester, α-carbomethoxy-cinnamic acid methyl esterα-cyano-β-methyl-p-methoxy-cinnamic acid methy; ester or butyl ester,α-carbomethoxy-p-methoxy-cinnamic acid methyl ester,N-(β-carbomethoxy-β-cyanovinyl)-2-methyl-indoline.

2.5 Nickel compounds, for example, nickel complexes of2,2'-thio-bis-[4-(1,1,3,3-tetramethylbutyl)-phenol], such as the 1:1 or1:2 complex, optionally with additional ligands such as n-butylamine,triethanolamine or N-cyclohexyl-diethanolamine, nickeldibutyldithiocarbamate, nickel salts of4-hydroxy-3,5-di-tert-butylbenzylphosphonic acid monoalkyl esters, suchas of the methyl, ethyl or butyl ester, nickel complexes of ketoximessuch as of 2-hydroxy-4-methyl-phenyl undecyl ketoxime, nickel complexesof 1-phenyl-4-lauroyl-5-hydroxy-pyrazole, optionally with additionalligands.

2.6. Sterically hindered amines, for examplebis-(2,2,6,6-tetramethylpiperidyl) sebacate,bis-(1,2,2,6,6-pentamethylpiperidyl) sebacate,n-butyl-3,5-di-tert.butyl-4-hydroxybenzyl malonic acidbis-(1,2,2,6,6-pentamethylpiperidyl)ester, condensation product of1-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinicacid, condensation product ofN,N'-(2,2,6,6-tetramethylpiperidyl)-hexamethylenediamine and4-tert-octylamino-2,6-dichloro-s-triazine,tris-(2,2,6,6-tetramethylpiperidyl)-nitrilotriacetate,tetrakis-(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butanetetracarbonicacid, 1,1'(1,2-ethanediyl)-bis-(3,3,5,5-tetramethylpiperazinone).

2.7. Oxalic acid diamides, for example, 4,4'-di-octyloxyoxanilide,2,2'-di-octyloxy-5,5'-di-tert-butyl-oxanilide,2,2'-di-dodecyloxy-5,5'-di-tert-butyl-oxanilide,2-ethoxy-2'-ethyl-oxanilide, N,N'-bis (3-dimethylaminopropyl)-oxalamide,2-ethoxy-5-tert-butyl-2'-ethyloxanilide and its mixture with2-ethoxy-2'-ethyl-5,4'-di-tert-butyloxanilide and mixtures of ortho- andpara-methoxy-as well as of o- and p-ethoxy-disubstituted oxanilides.

2.8. Hydroxyphenyl-s-triazines, for example2,6-bis-(2,4-dimethylphenyl)-4-(2-hydroxy-4-octyloxyphenyl)-s-triazine;2,6-bis-(2,4-dimethylphenyl)-4-(2,4-dihydroxyphenyl)-s-triazine;2,4-bis(2,4-dihydroxyphenyl)-6-(4-chlorophenyl)-s-triazine;2,4-bis[2-hydroxy-4-(2-hydroxyethoxy)phenyl]-6-(4-chlorophenyl)-s-triazine;2,4-bis[2-hydroxy-4-(2-hydroxyethoxy)phenyl-6-phenyl-s-triazine;2,4-bis[2-hydroxy-4-(2-hydroxyethoxy)phenyl]-6-(2,4-dimethylphenyl)-s-triazine;2,4-bis[2-hydroxy-4-(2-hydroxyethoxy)phenyl]-6-(4-bromophenyl)-s-triazine;2,4-bis[2-hydroxy-4-(2-acetoxyethoxy)phenyl]-6-(4-chlorophenyl)-s-triazine,2,4-bis(2,4-dihydroxyphenyl)-6-(2,4-dimethylphenyl)-s-triazine.

3. Metal deactivators, for example, N,N'-diphenyloxalic acid diamide,N-salicylal-N'-salicyloylhydrazine, N,N'-bis-salicyloylhydrazine,N,N'-bis-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hydrazine,3-salicyloylamino-1,2,4-triazole, bis-benzylidene-oxalic aciddihydrazide.

4. Phosphites and phosphonites, for example, triphenyl phosphite,diphenylalkyl phosphites, phenyldialkyl phosphites, tri-(nonylphenyl)phosphite, trilauryl phosphite, trioctadecyl phosphite,di-stearyl-pentaerythritol diphosphite, tris-(2,4-di-tert-butylphenyl)phosphite, di-isodecylpentaerythritol diphosphite,di-(2,4-di-tert-butylphenyl)pentaerythritol diphosphite,tristearylsorbitol triphosphite, tetrakis-(2,4-di-tert-butylphenyl)4,4'-diphenylylenediphosphonite.

5. Compounds which destroy peroxide, for example, esters ofβ-thiodipropionic acid, for example the lauryl, stearyl, myristyl ortridecyl esters, mercapto-benzimidazole or the zinc salt of2-mercaptobenzimidazole, zinc dibutyl-dithiocarbamate, dioctadecyldisulfide, pentaerythritol tetrakis-(β-dodecylmercapto)-propionate.

6. Hydroxylamines, for example, N,N-dibenzylhydroxylamine,N,N-diethylhydroxylamine, N,N-dioctylhydroxylamine,N,N-dilaurylhydroxylamine, N,N-ditetradecylhydroxylamine,N,N-dihexadecylhydroxylamine, N,N-dioctadecylhydroxylamine,N-hexadecyl-N-octadecylhydroxylamine,N-heptadecyl-N-octadecylhydroxylamine, N,N-dialkylhydroxylamine derivedfrom hydrogenated tallow amine.

7. Polyamide stabilizers, for example copper salts in combination withiodides and/or phosphorus compounds and salts of divalent manganese.

8. Basic co-stabilizers, for example, melamine, polyvinylpyrrolidone,dicyandiamide, triallyl cyanurate, urea derivatives, hydrazinederivatives, amines, polyamides, polyurethanes, alkali metal salts andalkaline earth metal salts of higher fatty acids for example Castearate, Zn stearate, Mg stearate, Na ricinoleate and K palmitate,antimony pyrocatecholate or zinc pyrocatecholate.

9. Nucleating agents, for example, 4-tert-butyl-benzoic acid, adipicacid, diphenylacetic acid.

10. Fillers and reinforcing agents, for example, calcium carbonate,silicates, glass fibers, asbestos, talc, kaolin, mica, barium sulfate,metal oxides and hydroxides, carbon black, graphite.

11. Other additives, for example, plasticizers, lubricants, emulsifiers,pigments, optical brighteners, flameproofing agents, anti-static agents,blowing agents and thiosynergists such as dilauryl thiodipropionate ordistearyl thiodipropionate.

Of particular interest is the utilization of the instant derivatives ina variety of coating systems including ambient cured and acid catalyzedcoating systems. In particular, the physical integrity of the coatingsis maintained to a higher degree with significant reduction in loss ofgloss and yellowing. Key improvements include the substantial absence ofthe cure retardation encountered with N-alkyl hindered amine lightstabilizers; the substantial absence of flocculation and dispersiondestabilization seen when N-alkyl hindered amines are utilized incertain pigmented coating systems and the absence of adhesion lossbetween the coating and polycarbonate substrate. Accordingly, thepresent invention also relates to the use of the instant compounds,optionally together with further stabilizers, for stabilizing ambientcured coatings based on alkyd resins; thermoplastic acrylic resins;acrylic alkyds; acrylic alkyd or polyester resins optionally modifiedwith silicon, isocyanates, isocyanurates, ketimines or oxazolidines; andepoxide resins crosslinked with carboxylic acids, anhydrides, polyaminesor mercaptans; and acrylic and polyester resin systems modified withreactive groups in the backbone thereof and crosslinked with epoxides;against the degradative effects of light, moisture and oxygen.

Furthermore, in their industrial uses, enamels with high solids contentbased on crosslinkable acrylic, polyester, urethane or alkyd resins arecured with an additional acid catalyst. Light stabilizers containing abasic nitrogen group are generally less than satisfactory in thisapplication. Formation of a salt between the acid catalyst and the lightstabilizer leads to incompatibility or insolubility and precipitation ofthe salt and to a reduced level of cure and to reduced light protectiveaction and poor resistance to moisture.

These acid catalyzed stoving lacquers are based on hot crosslinkableacrylic, polyester, polyurethane, polyamide or alkyd resins. The acrylicresin lacquers, which can be stabilized against light, moisture andoxygen in accordance with the invention, are the conventional acrylicresin stoving lacquers or thermosetting resins includingacrylic/melamine systems which are described, for example, in H.Kittel's "Lehrbuch der Lacke und Beschichtungen", Vol. 1 Par 2, on pages735 and 742 (Berlin 1972), "Lackkunstharze" (1977), by H. Wagner and H.F. Sarx, on pages 229-238, and in S. Paul's "Surface Coatings: Scienceand (1985).

The polyester lacquers, which can be stabilized against the action oflight and moisture, are the conventional stoving lacquers described e.g.in H. Wagner and H. F. Sarx, op. cit., on pages 86-99.

The alkyd resin lacquers which can be stabilized against the action oflight and moisture in accordance with the invention, are theconventional stoving lacquers which are used in particular for coatingautomobiles (automobile finishing lacquers), for example lacquers basedon alkyd/melamine resins and alkyd/acrylic/melamine resins (see H.Wagner and H. F. Sarx, op. cit., pages 99-123). Other crosslinkingagents include glycoluril resins, blocked isocyanates or epoxy resins.

The acid catalyzed stoving lacquers stabilized in accordance with theinvention are suitable both for metal finish coatings and solid shadefinishes, especially in the case of retouching finishes, as well asvarious coil coating applications. The lacquers stabilized in accordancewith the invention are preferably applied in the conventional manner bytwo methods, either by the single-coat method or by the two-coat method.In the latter method, the pigment-containing base coat is applied firstand then a covering coat of clear lacquer over it.

It is also to be noted that the instant substituted hindered amines areapplicable for use in non-acid catalyzed thermoset resins such as epoxy,epoxy-polyester, vinyl, alkyd, acrylic and polyester resins, optionallymodified with silicon, isocyanates or isocyanurates. The epoxy andepoxy-polyester resins are crosslinked with conventional crosslinkerssuch as acids, acid anhydrides, amines, and the like.

Correspondingly, the epoxide may be utilized as the crosslinking agentfor various acrylic or polyester resin systems that have been modifiedby the presence of reactive groups on the backbone structure.

To attain maximum light stability in such coatings, the concurrent useof other conventional light stabilizers can be advantageous. Examplesare the aforementioned UV absorbers of the benzophenone, benzotriazole,acrylic acid derivative, or oxanilide type, or aryl-s-triazines ormetal-containing light stabilizers, for example organic nickelcompounds. In two-coat systems, these additional light stabilizers canbe added to the clear coat and/or the pigmented base coat.

If such combinations are employed, the sum of all light stabilizers is0.2 to 20% by weight, preferably 0.5 to 5% by weight, based on thefilm-forming resin.

Examples of different classes of UV absorbers which may be used in theinstant compositions in conjunction with the aforementioned piperidinecompounds are referenced in a paper by H. J. Heller in European PolymerJournal Supplement, 1969, pp. 105-132. These classes include the phenylsalicylates, the o-hydroxybenzophenones, the hydroxyxanthones, thebenzoxazoles, the benzimidazoles, the oxadiazoles, the triazoles, thepyrimidines, the chinazolines, the s-triazines, thehydroxyphenyl-benzotriazoles, the alpha-cyanoacrylates and thebenzoates.

Types of UV absorbers of especial importance are:

(a) 2-(2'-Hydroxyphenyl)-benzotriazoles, for example, the 5'-methyl-,3',5'-di-tert-butyl-, 5'-tert-butyl-, 5-(1,1,3,3-tetramethylbutyl)-,5-chloro-3',5'-di-tert-butyl-, 5-chloro-3'-tert-butyl-5'-methyl-,3'-sec-butyl-5'-tert-butyl-, 4'-octoxy-, and 3',5'-di-tert-amylderivatives.

(b) 2-Hydroxy-benzophenones, for example, the 4-hydroxy-, 4-methoxy-,4-octoxy-, 4-decyloxy-, 4-dodecyloxy-, 4-benzyloxy, 4,2',4'-trihydroxy-and 2'-hydroxy-4,4'-dimethoxy derivatives.

(c) Acrylates, for example, alpha-cyano-β-β-diphenylacrylic acid ethylester or isoctyl ester, alpha-carbomethoxy-cinnamic acid methyl ester,alpha-cyano-β-methyl-p-methoxy-cinnamic acid methyl ester or butylester, alpha-carbomethoxy-p-methoxy-cinnamic acid methyl ester,N-(β-carbomethoxy-β-cyanovinyl)-2-methyl-indoline.

(d) Nickel compounds, for example, nickel complexes of2,2'-thiobis-[4-(1,1,3,3-tetramethylbutyl)-phenol], such as the 1:1 or1:2 complex, optionally with additional ligands such as n-butylamine,triethanolamine or N-cyclohexyl-diethanolamine, nickeldibutyldithiocarbamate, nickel salts of4-hydroxy-3,5-di-tert-butylbenzylphosphonic acid monoalkyl esters, suchas of the methyl, ethyl or butyl ester, nickel complexes of ketoximessuch as of 2-hydroxy-4-methyl-phenyl undecyl ketonoxime, nickelcomplexes of 1-phenyl-4-lauroyl-5-hydroxy-pyrazol, optionally withadditional ligands.

(e) Oxalic acid diamides, for example, 4,4'-di-octyloxyoxanilide,2,2'-di-octyloxy-5,5'-di-tert-butyl-oxanilide,2,2'-di-dodecyloxy-5,5'-di-tert-butyl-oxanilide,2-ethoxy-2'-ethyl-oxanilide, N,N'-bis-(3-dimethylaminopropyl)-oxalamide,2-ethoxy-5-tert-butyl-2'-ethyl-oxanilide and its mixture with2-ethoxy-2'-ethyl-5,4'-di-tert-butyl-oxanilide and its mixtures ofortho- and para-methoxy- as well as of o- and p-ethoxy-disubstitutedoxanilides.

(f) Hydroxyphenyl-s-triazines such as2,6-bis(2,4-di-methylphenyl)-4-(2-hydroxy-4-octyloxyphenyl)-s-triazineor the corresponding 4-(2,4-dihydroxyphenyl) derivative.

Of particular value in the instant compositions are the benzotriazolesof high molecular weight and low volatility such as2-[2-hydroxy-3,5-di(alpha,alpha-di-methylbenzyl)-phenyl]-2H-benzotriazole,2-(2-hydroxy-3,5-di-tert-octylphenyl)-2H-benzotriazole,2-(2-hydroxy-3-alpha,alpha-dimethylbenzyl-5-tert-octyl-phenyl)-2H-benzotriazole,2-(2-hydroxy-3-tert-octyl-5-alpha,alpha-dimethylbenzylphenyl)-2H-benzotriazole,2-(2-hydroxy-3,5-di-tert-amylphenyl)-2H-benzotriazole,2-[2-hydroxy-3-tert-butyl-5-(2-(omega-hydroxy-octa-(ethyleneoxy)carbonyl)-ethylphenyl]-2H-benzotriazole,dodecylated 2-(2-hydroxy-5-methylphenyl)-2H-benzotriazole,2-[2-hydroxy-3-tert-butyl-5-(2-octyloxycarbonyl)ethylphenyl]-2H-benzotriazoleand the 5-chloro compounds corresonding to each of the above namedbenzotriazoles.

Most preferably the benzotriazoles useful in the instant compositionsare2-[2-hydroxy-3,5-di(alpha,alpha-dimethyl-benzyl)phenyl]-2H-benzotriazole,dodecylated 2-(2-hydroxy-5-methylphenyl)-2H-benzotriazole,2-[2-hydroxy-3-tert-butyl-5-(2-(omega-hydroxy-octa-(ethyleneoxy)carbonyl)-ethylphenyl]-2H-benzotriazole,2-[2-hydroxy-3-tert-butyl-5-(2-octyloxycarbonyl)ethylphenyl]-2H-benzotriazoleand5-chloro-2-[2-hydroxy-3-tert-butyl-5-(2-octyloxycarbonyl)ethylphenyl]-2H-benzotriazole.

It is also contemplated that the instant compounds will be particularlyeffective as stabilizers for polyolefin fibers, especially polypropylenefibers, when used in conjunction with other stabilizers selected fromthe group consisting of the phenolic antioxidants, hindered amine lightstabilizers, organic phosphorus compounds, ultraviolet absorbers andmixtures thereof.

A further preferred embodiment of the instant invention is a stabilizedcomposition containing components (a), (b) and (c) described above whichadditionally contains as component (d) a phosphite or phosphonite.

The amount of phosphite or phosphonite (d) which is used in the instantcompositions is from 0.05 to 2% by weight, preferably from 0.1 to 1% byweight, based on the film forming resin. In two-coat systems, thesestabilizers may be added to the clear coat and/or base coat.

Typical phosphite and phosphonites include triphenyl phosphite,diphenylalkyl phosphites, phenyldialkyl phosphites,tri-(nonylphenyl)phosphite, trilauryl phosphite trioctadecyl phosphite,di-stearyl-pentaerythritol diphosphite, tris-(2,4-di-tert.butylphenyl)phosphite, di-isodecylpentaerythritol diphosphite,di-(2,4-di-tert.butylphenyl)pentaerythritol diphosphite,tristearyl-sorbitol triphosphite,tetrakis-(2,4-di-tert.butylphenyl)-4,4'-di-phenylylenediphosphonite.

The acid catalyzed thermoset enamels must be stabilized in order tofunction acceptably in end-use applications. The stabilizers used arehindered amines, preferably those substituted on the N-atom by an inertblocking group in order to prevent precipitation of the basic aminestabilized with the acid catalyst with a concomitant retardation incure, optionally in combination with UV absorbers, such as thebenzotriazoles, benzophenones, substituted s-triazines, phenyl benzoatesor oxanilides.

The stabilizers are needed to impart greater retention of durability tothe cured enamels (as measured by 20° gloss, distinction of image,cracking or chalking); the stabilizers must not retard cure (normal bakefor auto finishes at 121° C. and low bake repair at 82° C. (as measuredby hardness, adhesion, solvent resistance and humidity resistance), theenamel should not yellow on curing and further color change on exposureto light should be minimized; the stabilizers should be soluble in theorganic solvents normally used in coating applications such as methylamyl ketone, xylene, n-hexyl acetate, alcohol and the like.

The instant hindered amine light stabilizers substituted on the N-atomby an O-substituted moiety fulfill each of these requirements andprovide alone or in combination with a UV-absorber outstanding lightstabilization protection to the cured acid catalyzed thermoset enamels.

A preferred embodiment of the instant invention pertains to stabilizedcompositions comprising

(a) an acid catalyzed thermoset coating or enamel based on hotcrosslinkable acrylic, polyester or alkyd resins,

(b) a NO-R₁ -substituted 2,2,6,6-tetralkylpiperidine compound, and

(c) a UV absorber selected from the group consisting of thebenzophenones, benzotriazoles, acrylic acid derivatives, organic nickelcompounds, aryl-s-triazines and oxanilides.

Further ingredients which the enamels or coatings can contain areantioxidants, for example those of the sterically hindered phenolderivatives, phosphorus compounds, such as phosphites, phosphines orphosphonites, plasticizers, levelling assistants, hardening catalysts,thickeners, dispersants or adhesions promoters.

Still another preferred combination of the instant stabilizers is with ahydroxylamine in order to protect polypropylene fibers from gas fading.

The following examples are for illustrative purposes only and are notintended to limit the scope of the instant invention in any mannerwhatsoever.

EXAMPLE 1 Bis-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)trans,trans-Muconate

A solution of 1.70 gram of dimethyl trans-transmuconate, 5.62 grams of1-cyclohexyloxy-2,2,6,6-tertramethylpiperidin-4-ol and 0.025 gram oflithium amide in 100 ml of toluene is heated under reflux with aDean-Stark trap for 8 hours. The reaction mixture is then diluted withethyl acetate, and then washed with water, brine and dried overanhydrous magnesium sulfate. Concentration under reduced pressurefollowed by chromatographic separation affords the title compound as awhite solid.

EXAMPLE 2 1-Cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl Ester ofCarboxy-terminated Polybutadiene (HYCAR 2000×162)

Oxalyl chloride (2.10 ml) is added to a solution of HYCAR 2000×162 (25.0grams) in 75 ml of toluene. After stirring at room temperature forovernight, the reaction mixture is concentrated under reduced pressureto remove excess oxalyl chloride. The residue is dissolved in 50 ml ofdry toluene and then treated with 3.06 grams of1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-ol and 1.8 ml oftriethylamine in 50 ml of toluene. After stirring overnight, thereaction mixture is filtered and concentrated under reduced pressure toafford the title compound as a light oil. Infrared and nmr analysesindicate complete reaction and incorporation of the hindered aminemoiety into the polymer.

EXAMPLE 3 1-Cyclohexyloxy-2,2,6,6-tetramethyl-4-acryloyloxypiperidine

A solution of 1.6 ml of acryloyl chloride in 20 ml of methylene chlorideis added to a stirred solution of 5.11 grams of1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-ol and 3.10 ml oftriethylamine in 20 ml of methylene chloride at 0° C. After stirring atroom temperature for 2 hours, the solvent is removed under reducedpressure. The residue is then purified by liquid chromatography toafford the title compound as a white solid with a melting point of49°-52° C.

Analysis: Calcd for C₁₈ H₃₁ NO₃ : C, 69.9; H, 10.1; N, 4.5. Found: C,70.0; H, 10.5; N, 4.5.

EXAMPLE 41-Cyclohexyloxy-2,2,6,6-tetramethyl-4-methacryloyloxypiperidine

The procedure of Example 3 is repeated using 5.11 grams of1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-ol, 2.0 ml ofmethacryloyl chloride and 3.10 ml of triethylamine in methylenechloride. The above-named product is isolated as a colorless oil.

Analysis: Calcd for C₁₉ H₃₃ NO₃ : C, 70.6; H, 10.3; N, 4.3. Found: C,71.0; H, 10.6; N, 4.3.

EXAMPLE 5 1-Methoxy-2,2,6,6-tetramethyl-4-acryloyloxypiperidine

The procedure of Example 3 is repeated using 3.51 grams of1-methoxy-2,2,6,6-tetramethylpiperidin-4-ol, 1.6 ml of acryloyl chlorideand 3.10 ml of triethylamine in methylene chloride. The above-namedproduct is isolated as a colorless liquid.

Analysis: Calcd for C₁₃ H₂₃ NO₃ : C, 64.7; H, 9.6; N, 5.8. Found: C,64.0; H, 9.8; N, 5.6.

1-Methoxy-4-methacryloyloxy-2,2,6,6-tetramethylpiperidine is made bysubstituting an equivalent amount of methacryloyl chloride in place ofacryloyl chloride.

EXAMPLE 6 1-Cyclohexyloxy-2,2,6,6-tetramethyl-4-acrylamidopiperidine

The procedure of Example 3 is repeated using 3.0 grams of4-amino-1-cyclohexyloxy-2,2,6,6-tetramethylpiperidine, 0.92 ml ofacryloyl chloride and 1.8 ml of triethylamine in methylene chloride. Thetitle compound is isolated as a white solid.

Analysis: Calcd for C₁₈ H₃₂ N₂ O₂ : C, 70.1; H, 10.5; N, 9.1. Found: C,70.5; H, 10.8; N, 9.0.

EXAMPLE 7N,N-Bis(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)-acrylamide

The title compound is obtained when in the procedure of Example 6 anequivalent amount of N,N-bis(1-cyclohexyl-oxy-2,2,6,6-tetramethylpiperidin-4-yl)amine is substituted for4-amino-1-cyclohexyloxy-2,2,6,6-tetramethylpiperidine.

EXAMPLE 8 1-Octyloxy-2,2,6,6-tetramethyl-4-acryloyloxypiperidine

The procedure of Example 3 is repeated using an equivalent amount of1-octyloxy-2,2,6,6-tetramethylpiperidin-4-ol in place of1-cyclohexyloxy-2,2,6,6-tetramethylpiperidine-4-ol to afford the titlecompound as a colorless liquid.

Analysis: Calcd for C₂₀ H₃₇ NO₃ : C, 70.8; H, 11.0; N, 4.1. Found: C,71.0; H, 10.8; N, 4.6.

EXAMPLE 9 4-Maleimido-1-cyclohexyloxy-2,2,6,6-tetramethylpiperidine

To a solution of 5.29 grams of4-amino-1-cyclohexyloxy-2,2,6,6-tetramethylpiperidine in 50 ml ofacetone is added dropwise over 10 minutes a solution of maleic anhydride(1.96 grams) in acetone. After heating under reflux for 30 minutes, theintermediate maleamic acid is obtained . A solution of the maleamicacid, sodium acetate (0.3 grams) and acetic anhdride (6.4 ml) is heatedat 80° C. for two hours. The solution is then concentrated under reducedpressure and the residue purified by liquid chromatography to afford thetitle compound as a white solid with a melting point of 135°-139° C.

Analysis: Calcd for C₁₉ H₃₀ N₂ O₆ : C, 68.2; H, 9.0; N, 8.4. Found: C,68.6; H..93; N, 8.4.

EXAMPLE 101-Cyclohexyloxy-2,2,6,6-tetramethyl-4-vinylbenzyloxypiperidine

A solution of 1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-ol (5.11grams in N,N-dimethylformamide) is added dropwise to a stirredsuspension of sodium hydride (0.88 gram of a 60% dispersion). Afterstirring reaction mixture at room temperature for one hour and at 60° C.for 30 minutes, a solution of vinylbenzyl chloride (3.05 grams) in 5 mlof DMF is added. The reaction mixture is heated at 75° C. for sevenhours. The reaction mixture is then concentrated under reduced pressureand the residue is partitioned between ethyl acetate and water. Theorganic layer is washed with water, dried over anhydrous magnesiumsulfate and then evaporated to give a yellow oil. Preparative liquidchromatography affords the title compound as a light yellow oil.

Analysis: Calcd for C₂₄ H₃₇ NO₂ : C, 77.6; H, 10.0; N, 3.8. Found: C,77.4; H, 10.2; N, 3.7.

EXAMPLE 11 1-Octyloxy-2,2,6,6-tetramethyl-4-acryloyloxypiperidine

To a solution of 10.0 grams of4-acryloyloxy-2,2,6,6-tetramethylpiperidin-1-oxyl in 150 ml of n-octaneis added 0.6 gram of molybdenum trioxide. The resulting suspension isheated under reflux with a Dean-Stark trap in place. A 70% aqueoussolution of tert-butyl hydroperoxide (17.0 grams) is added dropwise overa 30-minute period with removal of the azeotrope. After heating underreflux for eight hours, the colorless reaction mixture is cooled to roomtemperature and the suspended catalyst is removed by filtration. Thefiltrate is stirred with aqueous sodium bisulfite solution for one hour.The organic layer is washed with brine, dried over anhydrous magnesiumsulfate and then evaporated. Liquid chromatography on the residueaffords the title compound as a colorless liquid.

Analysis: Calcd for C₂₀ H₃₇ NO₃ : C, 70.8; H, 11.0; N, 4.1. Found: C,70.6; H, 11.1; N, 4.1.

EXAMPLE 12 4-Allyloxy-1-octyloxy-2,2,6,6-tetramethylpiperidine

Sodium hydride (2.65 grams, 110 mmol) is added to a solution of 30.0grams (105 mmol) of 4-hydroxy-1-octyloxy-2,2,6,6-tetramethylpiperidinein 150 ml of tetrahydrofuran under nitrogen. The reaction mixture isheated at reflux for three hours, cooled to 35° C., and treated with12.7 grams (110 mmol) of allyl bromide. The reaction mixture is heatedat reflux for one hour, then partitioned between ethyl acetate (150 ml)and water (50 ml). The organic layer is washed with saturated sodiumchloride solution (100 ml), dried over anhydrous magnesium sulrate, andconcentrated under reduced pressure. The residue is dissolved in heptane(50 ml) and passed through a pad of silica gel (eluent 5:1 heptane:ethylacetate). The crude product is purified by flash chromatography (silicagel; 9:1 heptane:ethyl acetate) to afford 23.9 grams (70% yield ) of thetitle compound as a colorless oil.

Analysis: Calcd for C₂₀ H₃₉ NO₂ : C, 73.8; H, 12.1; N, 4.3. Found: C,74.0; H, 12.7; N, 4.7.

EXAMPLE 13 1-Octyloxy-4-methacryloyloxy-2,2,6,6-tetramethylpiperidine

The procedure of Example 3 is repeated using1-octyloxy-4-hydroxy-2,2,6,6-tetramethylpiperidine, methacryloylchloride and triethylamine in methylene chloride to afford the titlecompound as a colorless oil. Analyses by nmr, ir and ms give dataconsistent with the desired structure.

Analysis: Calcd for C₂₁ H₃₉ NO₃ : C, 71.3; H, 11.1; N, 4.0. Found: C,71.3; H, 11.2; N, 4.2.

EXAMPLE 14 Light Stabilization of Polypropylene

This example illustrates the light stabilizing effectiveness of instantstabilizers.

Polypropylene powder (Himont Profax 6501) stabilized with 0.2% by weightof n-octadecyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate is thoroughlyblended with the indicated amount of additive. The blended materials arethen milled on a two-roll mill at 182° C. for five minutes, after whichtime the stabilized polypropylene is sheeted from the mill and allowedto cool. The milled polypropylene is then cut into pieces andcompression molded on a hydraulic press at 250° C. and 175 psi (1.2×10⁶Pa) into 5 mil (0.127 mm) films. The sample is exposed in a fluorescentsunlight/black light chamber until failure. Failure is taken as thehours required to reach 0.5 carbonyl absorbance by infrared spectroscopyon the exposed films.

    ______________________________________                                                      Additive                                                                      Concentration                                                                              FS/BL Test Results                                 Additive Compound of                                                                        (% by weight)                                                                              (hours to Failure)                                 ______________________________________                                        Base Resin    --            340                                               Example 1     0.1          1290                                               Example 2     0.1           460                                               Example 3     0.1          1150                                               Example 6     0.1          1010                                               Example 9     0.1          1580                                                Example 10   0.1          1090                                               ______________________________________                                    

EXAMPLE 15

A monomer composition comprising 23.5% butyl acrylate, 27% butylmethacrylate, 30% 2-hydroxyethyl acrylate, 15% styrene, 3% acrylic acidand 1.5% of the acrylate monomer prepared in Example 11 (all % valuesare by weight) and 0.4 phr of tert-amyl peroxy-O-(2-ethylhexyl)monoperoxy carbonate initiator is polymerized in refluxing xylene toform a stabilized acrylic polyol polymer having a molecular weight(MW_(n)) of 1300 and (MW_(w)) of 6000.

EXAMPLE 16

The stabilized acrylic polyol prepared in Example 15 is blended withsufficient unstabilized acrylic polyol, made by the same procedure ofExample 15, but with the 1.5% by weight acrylate monomer of Example 11being replaced with butyl acrylate, so that in the finalacrylic-melamine formulation described below there is 1% of the hinderedamine acrylate present based on total resin solids.

The acrylic-melamine formulation comprises (all values are in parts byweight) 70 parts of acrylic polyol mixture as described above, 18 partsof melamine (Cymel 303, American Cyanamid), 0.51 part of sulfonic acidcatalyst (DDBSA Cycat, 70% 600, American Cyanamid), 0.6 part of flow aid(FC 431 50% solids fluorocarbon, 3M) and 8.8 parts of methyl amylketone.

Thermoset acrylic enamels are prepared using the formulations citedabove.

Pieces of steel sheeting 4 in.×12 in. (9.16 cm×30.48 cm), coated with apolyester/epoxy primer, are then coated with a silver metallic base coatand finally with a clear finishing enamel. The basecoat is sprayed ontothe coated sheet to a thickness of about 0.9 mil (0.023 mm) and airdried for three minutes.

The clear finishing enamel is then sprayed onto the sheet to a thicknessof about 2 mils (0.05 mm). After air drying for ten minutes, the coatedsheets are baked for thirty minutes at 250° C. (121° C. The Knoophardness values of the baked coating is then determined.

    ______________________________________                                        Knoop Hardness of High Solid Acid Cured Coatings                              Light Stabilizer  Knoop                                                       Present (% by weight)                                                                           Hardness                                                    ______________________________________                                        Control           9.3                                                         1% Copolymer of   9.4                                                         Example 15                                                                    1% Copolymer of   9.1                                                         Example 15                                                                    plus 3% UV                                                                    absorber*                                                                     1% Copolymer of   1.0                                                         hindered amine                                                                having no N-OR.sub.1                                                          group**                                                                       ______________________________________                                         *2-(2-hydroxy-3,5-di-tert-amylphenyl)-2H-benzotriazole                        **acrylic polyol made from 1,2,2,6,6pentamethyl-4-acryloyloxypiperidine  

The effectiveness of cure is assessed from the Knoop hardness values.The higher numbers indicate greater hardness and better cure. Theinstant compounds having the N-hydrocarbyloxy group do not cause cureretardation as do compounds such as those having N-alkyl substitution.

After storage for 1 week in an air-conditioned room, these coated panelsare then weathered in a QUV exposure apparatus according to ASTM G-53/77using FS-40 bulbs.

    ______________________________________                                        20 Degree Gloss                                                               Acrylic                                                                       Polymer   Hours QUV Exposure (FS-40)                                          (% by wt.)                                                                              0     925    1500 1808 2419 3168 3476 4088                          ______________________________________                                        Control   93    86     82    57*                                              1% Copolymer                                                                            94    91     85   83   76    53*                                    of Example 15                                                                 Control plus                                                                            94    90     90   90   87   79   64   31                            3% UV                                                                         Absorber**                                                                    1% Copolymer                                                                            94    91     90   92   86   85   84   82                            of Example 15                                                                 plus 3% UV                                                                    Absorber**                                                                    ______________________________________                                         *indicates cracking                                                           **2(2-hydroxy-3,5-di-tert-amylphenyl)-2H-benzotriazole                   

EXAMPLE 17

A two component acrylic urethane refinish coating based on a polyolcomposed of monomers such as 2-hydroxyethyl acrylate, butyl acrylate,butyl methacrylate, styrene, and acrylic acid and an aliphaticisocyanate crosslinking resin (Desmodur N-3390 from Mobay Corp) in a1.05/1.00 ratio is formulated to include 1% by weight of hindered aminelight stabilizer.

Commercially available 4"×12" (10.16 cm×30.48 cm) steel panels (AdvancedCoatings Technology) are first primed with a commercial epoxy primer andthen spray coated with a thermoplastic silver metallic basecoat to athickness of about 0.8 mil (0.023 mm) and air dried for 5 minutes. Thestabilized acrylic urethane clearcoat is then sprayed onto the basecoatto thickness of 1.7 mil (0.049 mm). AFter storage for 1 month in anair-conditioned room, the coated panels are weathered in a Xenon ArcWeatherometer. Gloss and Distinction-of-image are measured at 300 hourintervals.

    ______________________________________                                        20 Degree Gloss                                                                         Xenon Exposure (180 cam)                                                      0 Hours  853 Hours  2019 Hours                                      Acrylic Polymer                                                                           20             20         20                                      (% by wt.)  Gloss   DOI    Gloss DOI  Gloss DOI                               ______________________________________                                        Control     89      83     24     4   20     5                                1% Copolymer of                                                                           89      76     78    46   39     9                                hindered amine                                                                having no N-OR                                                                group*                                                                        1% Copolymer of                                                                           89      90     86    73   51    13                                Example 15                                                                    1% Copolymer of                                                                           89      90     91    85   82    73                                Example 15 plus 3%                                                            UV Absorber **                                                                ______________________________________                                         *acrylic polyol made from 1,2,2,6,6pentamethyl-4-acryloyloxypiperidine        **2[2hydroxy-3-tert-butyl-5-(2-(omega-hydroxy-octa-(ethyleneoxy)-carbonyl    -ethylphenyl2H-benzotriazole                                              

EXAMPLE 18

A silver metallic alkyd enamel is stabilized with the indicated amountsof UV absorber and hindered amine derivative (by weight of total resinsolids) and then spray applied to a thickness of 2.75 mils onto panelsprimed with an epoxy amine primer. After the coated panels aged atambient temperature for one month, they are exposed in a Xenon ArcWeathermeter and 60 degree gloss is measured at 100 hour intervals.

    ______________________________________                                        60 Degree Gloss                                                                             Hours Xenon Exposure (180 cam)                                  Formulation (% by wt.)                                                                        0       473     1024  1542                                    ______________________________________                                        Unstabilized    90      30      13*   --                                      2% UV Absorber plus                                                                           90      63      24    18*                                     2% Compound of Example 9                                                      ______________________________________                                         *indicates cracking                                                           **2[2hydroxy-3-tert-butyl-5-(2-omega-hydroxy-octa-(ethyleneoxy)-carbonyl)    ethylphenyl2H-benzotriazole                                               

What is claimed is:
 1. A stabilized composition which comprises(A) anorganic polymer subject to the deleterious effects of actinic light, and(B₁) a stabilizing amount of an ethylenically unsaturated, polymerizablemonomer containing a hindered amine moiety substituted on the 1-N atomwith a hydroxycarbyloxy group, said moiety having the formula E##STR15## where L₁ and L₂ are independently alkyl of 1 or 4 carbonatoms, or L₁ and L₂ together are pentamethylene, and R₁ is hydrocarbyl,and said monomer is selected from the group consisting of formulas I-IX##STR16## where R₁ is alkyl of 1 to 36 carbon atoms, alkenyl of 2 to 18carbon atoms, alkynyl of 2 to 18 carbon atoms, aralkyl of 7 to 15 carbonatoms, cycloalkyl of 5 to 12 carbon atoms, cycloalkenyl of 5 to 12carbon atoms, a radical of a saturated or unsaturated bicyclic ortricyclic hydrocarbon of 7 to 12 carbon atoms, or aryl of 6 to 10 carbonatoms or said aryl substituted by alkyl,X is a direct bond,--O(polyoxyalkyleneO)-- of 2 to 12 carbon atoms, --O--, --NH-- or--NG--, where G is alkyl of 1 to 8 carbon atoms, X₁ is a direct bond or--O--, n is 1 or 2, T₁, R₂ and T₄ are independently hydrogen, halogen,alkyl of 1 to 18 carbon atoms or aryl of 6 to 10 carbon atoms, T₃ ishydrogen or methyl, and R₂, R₃ and R₄ are independently hydrogen oralkyl of 1 to 12 carbon atoms; or R₂ is also cyano in formula III; or(B₂) a stabilizing amount of polymer or copolymer which comprises thefree radical polymerization product of (a) 1 to 100% by weight, based onthe total polymer or copolymer, of at least one ethylenicallyunsaturated polymerizable monomer containing a hindered amine moietysubstituted on the 1-N atom with a hydrocarbyloxy group, said moietyhaving the formula E ##STR17## where L₁ and L₂ are independently alkylof 1 to 4 carbon atoms, or L₁ and L₂ together are pentamethylene, R ishydrogen or methyl, and R₁ is hydrocarbyl, and said monomer is selectedfrom the group consisting of formulas I-IX ##STR18## where R₁ is alkylof 1 to 36 carbon atoms, alkenyl of 2 to 18 carbon atoms, alkynyl of 2to 18 carbon atoms, aralkyl of 7 to 15 carbon atoms, cycloalkyl of 5 to12 carbon atoms, cycloalkenyl of 5 to 12 carbon atoms, a radical of asaturated or unsaturated bicyclic or tricyclic hydrocarbon of 7 to 12carbon atoms, or aryl of 6 to 10 carbon atoms or said aryl substitutedby alkyl,X is a direct bond, --O(polyoxyalkyleneO)--) of 2 to 12 carbonatoms, --O--, --NH-- or --NG--, where G is alkyl of 1 to 8 carbon atoms,X₁ is a direct bond or --O--, n is 1 or 2, T₁, R₂ and T₄ areindependently hydrogen, halogen, alkyl of 1 to 18 carbon atoms or arylof 6 to 10 carbon atoms, T₃ is hydrogen or methyl, and R₂, R₃ and R₄ areindependently hydrogen or alkyl of to 12 carbon atoms, or R₂ is alsocyano in formula III; and (b) 99 to 0% by weight, based on the totalpolymer or copolymer, of at least one ethylenically unsaturated,polymerizable monomer having no group of formula E present and selectedfrom the group consisting of the esters and amides of acrylic andmethacrylic acid, the itaconates, the citraconates, styrene, the vinylpyridines, divinylbenzene, acrylonitrile, methacrylonitrile,N-vinyl-2-pyrrolidone, N-vinylcarbazole, maleimides, vinyl sulfonate,vinyl phosphonates, alpha-olefins, isoprene, butadiene, vinyl esters,vinyl ethers and halogenated olefins.
 2. A composition according toclaim 1 wherein componeht (A) is a polyolefin.
 3. A compositionaccording to claim 2 wherein the polyolefin is polypropylene.
 4. Acomposition according to claim 1 wherein component (A) is an acrylicresin.
 5. A composition according to claim 1, wherein said organicmaterial is a coating system based on alkyd, acrylic, acrylic alkyd,polyester, epoxide, urethane, polyamide, vinyl or epoxy-polyesterresins.
 6. A composition according to claim 5 which contains a UVabsorber or additional light stabilizer.
 7. A method for stabilizing anorganic material against oxidative, thermal ora ctinic degradation whichcomprisesincorporating into said organic material an effectivestabilizing amount of an ethylenically unsaturated, polymerizablemonomer containing a hindered amine moiety substituted on the 1-N atomwith a hydrocarbyloxy group, said moiety having the formula E ##STR19##where L₁ and L₂ are independently alkyl of 1 to 4 carbon atoms, or L₁and L₂ together are pentamethylene, and R₁ is hydrocarbyl, and saidmonomer is selected from the group consisting of formulas I-IX ##STR20##where R₁ is alkyl of 1 to 36 carbon atoms, alkenyl of 2 to 18 carbonatoms, alkynyl of 2 to 18 carbon atoms, aralkyl of 7 to 15 carbon atoms,cycloalkyl of 5 to 12 carbon atoms, cycloalkenyl of 5 to 12 carbonatoms, a radical of a saturated or unsaturated bicyclic or tricyclichydrocarbon of 7 to 12 carbon atoms, or aryl of 6 to 10 carbon atoms orsaid aryl substituted by alkyl,X is a direct bond,--O(polyoxyalkyleneO)-- of 2 to 12 carbon atoms, --O--, --NH-- or--NG--, where G is alkyl of 1 to 8 carbon atoms, X₁ is a direct bond or--O--, n is 1 or 2, T₁, R₂ and T₄ are independently hydrogen, halogen,alkyl of 1 to 18 carbon atoms or aryl of 6 to 10 carbon atoms, T₃ ishydrogen or methyl, and R₂, R₃ and R₄ are independently hydrogen oralkyl of to 12 carbon atoms, or R₂ is also cyano in formula III.
 8. Amethod for stabiizing an organic material against oxidative, therml oractinic degradation which comprisesincorporating into said organicmaterial an effective stabiizing amount of a polymer or copolymer whichcomprises the polymerization product of (a) 1 to 100% by weight, basedon the total polymer or copolymer, of at least one ethylenicallyunsaturated, polymerizable monomer containing a hindered amine moietysubstituted on the 1-N atom with a hydrocarbyloxy group, said moietyhaving the formula E ##STR21## L₁ and L₂ are independnetly alkyl of 1 to4 carbon atoms, or L₁ and L₂ together are pentamethylene, and R₁ ishydrocarbyl, and said monomer is selected from the group consisting offormulas I-IX ##STR22## where R₁ is alkyl of 1 to 36 carbon atoms,alkenyl of 2 to 18 carbon atoms, alkynyl of 2 to 18 carbon atoms,aralkyl of 7 to 15 carbon atoms, cycloalkyl of 5 to 12 carbon atoms,cycloalkenyl of 5 to 12 carbon atoms, a radical of a saturated orunsaturated bicyclic or tricyclic hydrocarbon of 7 to 12 carbon atoms,or aryl of 6 to 10 carbon atoms or said aryl substituted by alkyl,X is adirect bond, --O(polyoxyalkyleneO)-- of 2 to 12 carbon atoms, --O--,--NH-- or --NG--, where G is alkyl of 1 to 8 carbon atoms, X₁ is adirect bond or --O--, n is 1 or 2, T₁, R₂ and T₄ are independentlyhydrogen, halogen, alkyl of 1 to 18 carbon atoms or aryl of 6 to 10carbon atoms, T₃ is hydrogen or methyl, and R₂, R₃ and R₄ areindependently hydrogen or alkyl of to 12 carbon atoms, or R₂ is alsocyano in formula III; (b) 99 to 0% by weight, based on the total polymeror copolymer, of at least one ethylenically unsaturated, polymerizablemonomer having no group of formula E present and selected from the groupconsisting of esters and amides of acrylic and methacrylic acid, theitaconates, the citraconates, styrene, the vinyl pyridines,divinylbenzene, acrylonitrile, methacrylonitrile, N-vinyl-2-pyrrolidone,N-vinylcarbazole, maleimides, vinyl sulfonate, vinyl phosphonates,alpha-olefins, isoprene, butadiene, vinyl esters, vinyl ethers andhalogenated olefins.